Search

Anxiety and epilepsy are common worldwide and represent a primary global health concern. Fisetin, a flavonoid isolated from Bauhinia pentandra, has a wide range of biological activities may be a promising alternative to combat diseases related to the central nervous system (CNS). The present study aimed to investigate the anxiolytic and anticonvulsant effects of fisetin on adult zebrafish. Furthermore, molecular docking simulations were performed to improve the results. Fisetin did not present toxicity and caused anxiolytic behavior and delayed seizures in animals. This effect may occur through serotonin neurotransmission at 5-HT3A and/or 5-HT3B receptors. Molecular docking simulations showed that fisetin interacts with the orthosteric site of the 5-HT3A receptor with strong H-bond interactions with the Trp156 residue, with a strong contribution from the catechol ring, a behavior similar to that of the antagonist co-crystallized inhibitor granisetron (CWB). Fisetin may be a promising alternative to combat diseases related to the central nervous system. Keywords anxiety • Bauhinia pentandra • Danio rerio • epilepsy • fisetin., (© 2024 Wiley‐VCH GmbH.)

Per- and polyfluoroalkyl substances (PFASs) have been detected in an array of environmental media due to their ubiquitous use in industrial and consumer products as well as potential release from fluorochemical manufacturing facilities. During their manufacture, many fluorotelomer (FT) facilities rely on neutral intermediates in polymer production including the FT-alcohols (FTOHs). These PFAS are known to transform to the terminal acids (perfluoro carboxylic acids; PFCAs) at rates that vary with environmental conditions. In the current study on soils from a FT facility, we employed gas chromatography coupled with conventional- and high-resolution mass spectrometry (GC-MS and GC-HRMS) to investigate the profile of these precursor compounds, the intermediary secondary alcohols (sFTOHs), FT-acrylates (FTAcr), and FT-acetates (FTAce) in soils around the former FT-production facility. Of these precursors, the general trend in detection intensity was [FTOHs] > [sFTOHs] > [FTAcrs], while for the FTOHs, homologue intensities generally were [12:2 FTOH] > [14:2 FTOH] > [16:2 FTOH] > [10:2 FTOH] > [18:2 FTOH] > [20:2 FTOH] > [8:2 FTOH] ∼ [6:2 FTOH]. The corresponding terminal acids were also detected in all soil samples and positively correlated with the precursor concentrations. GC-HRMS confirmed the presence of industrial manufacturing byproducts such as FT-ethers and FT-esters and aided in the tentative identification of previously unreported dimers and other compounds. The application of GC-HRMS to the measurement and identification of precursor PFAS is in its infancy, but the methodologies described here will help refine its use in tentatively identifying these compounds in the environment.

Aim: Our objective was to investigate the trypanocidal effect of the chalcone (2 E ,4 E )-1-(2-hydroxy-3,4,6-trimethoxyphenyl)-5-phenylpenta-2,4-dien-1-one (CPNC). Material & methods: Cytotoxicity toward LLC-MK2 host cells was assessed by MTT assay, and the effect on Trypanosoma cruzi life forms (epimastigotes, trypomastigotes and amastigotes) was evaluated by counting. Flow cytometry analysis was performed to evaluate the possible mechanisms of action. Finally, molecular docking simulations were performed to evaluate interactions between CPNC and T. cruzi enzymes. Results: CPNC showed activity against epimastigote, trypomastigote and amastigote life forms, induced membrane damage, increased cytoplasmic reactive oxygen species and mitochondrial dysfunction on T. cruzi . Regarding molecular docking, CPNC interacted with both trypanothione reductase and TcCr enzymes. Conclusion: CPNC presented a trypanocidal effect, and its effect is related to oxidative stress, mitochondrial impairment and necrosis.

Chagas disease (CD) is a neglected tropical disease of worldwide health concern, caused by the flagellate protozoan Trypanosoma cruzi (T. cruzi), endemic in Latin America and present in North America and Europe. The WHO recommended drug for CD, benznidazole has low safety profile and several limitations. Therefore, an entity with better therapeutic potential to treat CD is required. Chalcones are an important class of compounds, which have shown antichagasic potential. Thus, the objective of this study was to evaluate the activity of synthetic p-aminochalcones against T. cruzi. Chalcones 1 and 2 were synthesized by Claisen-Schmidt condensation and characterized by both spectroscopic and theoretical methods. Initially, they were submitted to molecular docking simulations using cruzain and trypanothione reductase (TR) enzymes. It was expected to observe the possible interactions of chalcones with the catalytic site and other important regions of these main pharmacological targets of T. cruzi. Their cytotoxicity within host cells were assessed by MTT reduction assay using LLC-MK 2 cells, with CC 50  = 85.6 ± 9.2 µM and 1115 ± 381.7 µM for chalcones 1 and 2, respectively. These molecules were also tested against epimastigote and trypomastigote life forms of T. cruzi, causing reduction in the number of viable parasites. For the evaluation of the effect on intracellular amastigotes, infected LLC-MK2 cells were incubated with the chalcones for 24 h, causing reduction in the percentage of infected cells and the number of amastigotes/100 cells. Finally, flow cytometry assays were performed for analyzing cell death mechanisms (7-AAD/AxPE labelling), cytoplasmic ROS accumulation (DCFH-DA assay) and mitochondrial transmembrane potential disruption (Rho123 assay). Both chalcones (1 and 2) caused membrane damage, ROS accumulation and mitochondrial depolarization. In conclusion, the synthetic p-aminochalcones presented trypanocidal effect, causing membrane damage and oxidative stress. Their mechanism of action may be related to cruzain and TR inhibition., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Samples from 450 homes with shallow private wells throughout the state of Wisconsin (USA) were collected and analyzed for 44 individual per- and polyfluoroalkyl substances (PFAS), general water quality parameters, and indicators of human waste as well as agricultural influence. At least one PFAS was detected in 71% of the study samples, and 22 of the 44 PFAS analytes were detected in one or more samples. Levels of PFOA and/or PFOS exceeded the proposed Maximum Contaminant Levels of 4 ng/L, put forward by the U.S. Environmental Protection Agency (EPA) in March 2023, in 17 of the 450 samples, with two additional samples containing PFHxS ≳ 9 ng/L (the EPA-proposed hazard index reference value). Those samples above the referenced PFAS levels tend to be associated with developed land and human waste indicators (artificial sweeteners and pharmaceuticals), which can be released to groundwater via septic systems. For a few samples with levels of PFOA, PFOS, and/or PFHxS > 40 ng/L, application of wastes to agricultural land is a possible source. Overall, the study suggests that human waste sources, septic systems in particular, are important sources of perfluoroalkyl acids, especially ones with ≤8 perfluorinated carbons, in shallow groundwater.

Access to a clean and healthy environment is a human right and a prerequisite for maintaining a sustainable ecosystem. Experts across domains along the chemical life cycle have traditionally operated in isolation, leading to limited connectivity between upstream chemical innovation to downstream development of water-treatment technologies. This fragmented and historically reactive approach to managing emerging contaminants has resulted in significant externalized societal costs. Herein, we propose an integrated data-driven framework to foster proactive action across domains to effectively address chemical water pollution. By implementing this integrated framework, it will not only enhance the capabilities of experts in their respective fields but also create opportunities for novel approaches that yield co-benefits across multiple domains. To successfully operationalize the integrated framework, several concerted efforts are warranted, including adopting open and FAIR (findable, accessible, interoperable, and reusable) data practices, developing common knowledge bases/platforms, and staying vigilant against new substance "properties" of concern., Competing Interests: DECLARATION OF INTERESTS The authors declare no competing interests.

Trypanosoma theileri is a worldwide distributed haemoparasite that has been reported throughout the American continent in various species, including bovines, buffaloes and bats. In bovines, high incidence of T. theileri can be harmful when associated with other infections or under stress situations. There is little information on this hemoflagellate in Ecuador, which prompted the study and molecular identification of the trypanosomes collected in two slaughtering centers. Between February and April 2021, a total of 218 samples of bovine blood were collected in abattoirs located in the Andean region of Quito ( n = 83) and in the coastal region, in Santo Domingo ( n = 135). Quito public Slaughterhouse is the biggest in Ecuador, and for that, they receive animals from all country; on the other hand, Santo Domingo's Slaughterhouse is a small one where mainly females from the region are sacrificed and some males. The samples were evaluated using two molecular tests, the PCR cathepsin L-like (CatL) specific for T. theileri and for the positive samples, a Nested PCR that targets the ITS of the 18S gene. The corresponding PCR products were sequenced, analyzed by BLAST/NCBI and the sequences were used to build a concatenated phylogenetic tree, using the MEGA XI software. Overall, 34 out of the 218 samples, (15.6%) were positive to T. theileri by PCR CatL, resulting from 20/83 (24.1%) positives from the Quito abattoir and 14/135 (10.4%) from the Santo Domingo slaughterhouse. These prevalence rates were found to be significantly different ( p = 0.006). According to the phylogenetic tree based on the CatL and ITS concatenated sequences ( n = 13), the two novel Equatorial T. theileri isolates, ThI ( n = 7) and ThII ( n = 6) are closely related and associated to the IC, IB and IIB genotypes, present in Brazil, Venezuela and Colombia. Thirty-one out of the thirty-four T. theileri-positive bovines were co-infected with other haemotropic pathogens, Anaplasma marginale Babesia spp and T. vivax . This coinfection could be responsible for additional pathologies and harmful effects on the affected cattle. This study presents the molecular identification and genotypification of T. theileri isolated from cattle in Ecuador through the analysis of CAtL and ITS sequences, and the high frequency of coinfection of this hemoflagellate with other blood haemotropic organisms., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Chávez-Larrea, Cholota-Iza, Cueva-Villavicencio, Yugcha-Díaz, Ron-Román, Rodríguez-Cabezas, Saegerman and Reyna-Bello.)

Per- and polyfluoroalkyl substances (PFAS) are globally distributed and potentially toxic compounds. We report accumulation of chloroperfluoropolyethercarboxylates (Cl-PFPECAs) and perfluorocarboxylates (PFCAs) in vegetation and subsoils in New Jersey. Lower molecular weight Cl-PFPECAs, containing 7-10 fluorinated carbons, and PFCAs containing 3-6 fluorinated carbons were enriched in vegetation relative to surface soils. Subsoils were dominated by lower molecular weight Cl-PFPECAs, a divergence from surface soils. Contrastingly, PFCA homologue profiles in subsoils were similar to surface soils, likely reflecting temporal-use patterns. Accumulation factors (AFs) for vegetation and subsoils decreased with increasing CF 2 , 6-13 for vegetation and 8-13 in subsoils. In vegetation, for PFCAs having CF 2 = 3-6, AFs diminished with increasing CF 2 as a more sensitive function than for longer chains. Considering that PFAS manufacturing has transitioned from long-chain chemistry to short-chain, this elevated vegetative accumulation of short-chain PFAS suggests the potential for unanticipated PFAS exposure levels globally in human and/or wildlife populations. This inverse relationship between AFs and CF 2 -count in terrestrial vegetation is opposite the positive relationship reported in aquatic vegetation suggesting aquatic food webs may be preferentially enriched in long-chain PFAS. AFs normalized to soil-water concentrations increased with chain length for CF 2 = 6-13 in vegetation but remained inversely related to chain length for CF 2 = 3-6, reflecting a fundamental change in vegetation affinity for short chains compared to long.

Objective: Mobile health technology offers promise for reducing disparities in pediatric asthma care and outcomes by helping parents more effectively communicate with their children's primary care providers and manage their children's asthma. This study tested the impact of a text messaging program on emergency department utilization and asthma morbidity., Methods: A randomized controlled trial enrolled 221 parents of Medicaid-insured children visiting the emergency departments of 2 urban children's hospitals in the Pacific Northwest for an asthma-related concern between September 2015 and February 2019. Standardized surveys were administered to parents at baseline and 12 months later to assess the primary outcomes of emergency department utilization and morbidity as well as primary care utilization, parent communication self-efficacy, and asthma self-management knowledge. The intervention group received brief in-person education on partnering with primary care providers, followed by 3 months of educational text messages., Results: Participants were mostly female, English speakers, of minority race and ethnicity, and living below 200% of the federal poverty level. Negative binomial and linear regressions indicated no significant group differences in annual number of emergency department visits, morbidity, parent communication self-efficacy, or asthma self-management knowledge at 12 months' follow-up, adjusting for baseline covariates. Average annual rate of primary care visits for asthma was 35% higher in the intervention group compared to control group at follow-up (95% confidence interval 1.03-1.76, P = .03)., Conclusions: This parent-focused text message intervention did not impact emergency department utilization or asthma morbidity; however, results suggest its potential for enhancing use of primary care for management of pediatric chronic conditions., (Copyright © 2022 Academic Pediatric Association. Published by Elsevier Inc. All rights reserved.)

Background: Antimicrobial resistance is a growing health problem worldwide. One strategy to face this problem in a reasonable way is training health personnel for the rational use of antimicrobials. There are some difficulties associated with medical staff to receiving training with E-learning education, but there is a lack of studies and insufficient evidence of the effectiveness of this method compared to face-to-face learning. Methods: An educational intervention on antimicrobial resistance (AMR) and antimicrobial prescription practice (APP) was designed and implemented using two approaches: face-to-face and E-learning among physicians of the intensive care unit (ICU) and internal medicine ward (IMW) at Eugenio Espejo Hospital in Quito. Modalities of interventions were compared to propose a strategy of continuous professional development (CPD) for all hospital staff. An interventional study was proposed using a quasi-experimental approach that included 91 physicians, of which 49 belong to the IMW and 42 to the ICU. All of them received training on AMR—half in a face-to-face mode and the other half in an asynchronous E-learning mode. They then all participated on APP training but with switched groups; those who previously participated in the face-to-face experience participated in an E-learning module and vice-versa. We evaluated self-perception about basic knowledge, attitudes and referred practices towards AMR and APP before and after the intervention. A review of medical records was conducted before and after training by checking antimicrobial prescriptions for all patients in the ICU and IMW with bacteremia, urinary tract infection (UTI), pneumonia, and skin and soft tissue infection. The study received IRB clearance, and we used SPSS for statistical analysis. Results: No statistically significant difference was observed between the E-learning and the face-to-face methodology for AMR and APP. Both methodologies improved knowledge, attitudes and referred practices. In the case of E-learning, there was a self-perception of improved attitudes (p < 0.05) and practices (p < 0.001) for both AMR and APP. In face-to-face, there was a perception of improvement only in attitudes (p < 0.001) for APP. In clinical practice, the use of antimicrobials significantly improved in all domains after training, including empirical and targeted treatment of bacteremia and pneumonia (p < 0.001) and targeted treatment of UTI (p < 0.05). For the empirical treatment of pneumonia, the mean number of antibiotics was reduced from 1.87 before to 1.05 after the intervention (p = 0.003), whereas in the targeted management of bacteremia, the number of antibiotics was reduced from 2.19 to 1.53 (p = 0.010). Conclusions: There was no statistically significant difference between the effect of E-learning and face-to-face strategy in terms of teaching AMR and APP. Adequate self-reported attitudes and practices in E-learning exceed those of the face-to-face approach. The empiric and targeted use of antimicrobials improved in all reviewed cases, and we observed an overall decrease in antibiotic use. Satisfaction with training was high for both methods, and participants valued the flexibility and accessibility of E-learning.

Although next-generation per- and polyfluorinated substances (PFAS) were designed and implemented as safer and environmentally degradable alternatives to "forever" legacy PFAS, there is little evidence to support the actual transformation of these compounds and less evidence of the safety of transformed products in the environment. Multiple congeners of one such PFAS alternative, the chloro-perfluoropolyether carboxylates (Cl-PFPECAs), have been found in New Jersey soils surrounding a manufacturing facility. These compounds are ideal candidates for investigating environmental transformation due to the existence of potential reaction centers including a chlorinated carbon and ether linkages. Transformation products of the chemical structures of this class of compounds were predicted based on analogous PFAS transformation pathways documented in peer-reviewed literature. Potential reaction products were used as the basis for high-resolution mass-spectrometric suspect screening of the soils. Suspected transformation products of multiple congeners, the Cl-PFPECAs, including H-PFPECAs, epox-PFPECAs, and diOH-PFPECAs, were tentatively observed in these screenings. Although ether linkages have been hypothesized as potential reaction centers under environmental conditions, to date, no documentation of ether scission has been identified. Despite exhaustive scrutiny of the high-resolution data for our Cl-PFPECA-laden soils, we found no evidence of ether scission.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in many consumer applications due to their stain repellency, surfactant properties, ability to form water-proof coatings and use in fire suppression. The production, application, transport, use and disposal of PFAS and PFAS-treated products have resulted in their wide-spread occurrence in environmental and biological systems. Concern over exposure to PFAS and their transformation products and metabolites has necessitated the development of tools to predict the transformation of PFAS in environmental systems and metabolism in biological systems. We have developed reaction libraries for predicting transformation products and metabolites in a variety of environmental and biological reaction systems. These reaction libraries are based on generalized reaction schemes that encode the process science of PFAS reported in the peer-reviewed literature. The PFAS reaction libraries will be executed through the Chemical Transformation Simulator, a web-based tool that is available to the public. These reaction libraries are intended for predicting the environmental transformation and metabolism of PFAS only.

Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

Background: Chikungunya virus (CHIKV) emerged in the Americas in 2013 and has caused approximately 2.1 million cases and >600 deaths. A retrospective investigation was undertaken to describe clinical, epidemiological, and viral genomic features associated with deaths caused by CHIKV in Ceará state, northeast Brazil., Methods: Sera, cerebrospinal fluid (CSF), and tissue samples from 100 fatal cases with suspected arbovirus infection were tested for CHIKV, dengue virus (DENV), and Zika virus (ZIKV). Clinical, epidemiological, and death reports were obtained for patients with confirmed CHIKV infection. Logistic regression analysis was undertaken to identify independent factors associated with risk of death during CHIKV infection. Phylogenetic analysis was conducted using whole genomes from a subset of cases., Results: Sixty-eight fatal cases had CHIKV infection confirmed by reverse-transcription quantitative polymerase chain reaction (52.9%), viral antigen (41.1%), and/or specific immunoglobulin M (63.2%). Co-detection of CHIKV with DENV was found in 22% of fatal cases, ZIKV in 2.9%, and DENV and ZIKV in 1.5%. A total of 39 CHIKV deaths presented with neurological signs and symptoms, and CHIKV-RNA was found in the CSF of 92.3% of these patients. Fatal outcomes were associated with irreversible multiple organ dysfunction syndrome. Patients with diabetes appear to die at a higher frequency during the subacute phase. Genetic analysis showed circulation of 2 CHIKV East-Central-South African (ECSA) lineages in Ceará and revealed no unique virus genomic mutation associated with fatal outcome., Conclusions: The investigation of the largest cross-sectional cohort of CHIKV deaths to date reveals that CHIKV-ECSA strains can cause death in individuals from both risk and nonrisk groups, including young adults., (© The Author(s) 2020. Published by Oxford University Press for the Infectious Diseases Society of America.)

Introduction: Despite the exalted status of sputum mycobacterial load for gauging pulmonary tuberculosis treatment and progress, Chest X-rays supplement valuable information for taking instantaneous therapeutic decisions, especially during the COVID-19 pandemic. Even though literature on individual parameters is overwhelming, few studies have explored the interaction between radiographic parameters denoting severity with mycobacterial burden signifying infectivity. By using a sophisticated approach of integrating Chest X-ray parameters with sputum mycobacterial characteristics, evaluated at all the three crucial time points of TB treatment namely pre-treatment, end of intensive phase and completion of treatment, utilizing the interactive Cox Proportional Hazards model, we aimed to precisely deduce predictors of unfavorable response to TB treatment., Materials and Method: We extracted de-identified data from well characterized clinical trial cohorts that recruited rifampicin-sensitive Pulmonary TB patients without any comorbidities, taking their first spell of anti-tuberculosis therapy under supervision and meticulous follow up for 24 months post treatment completion, to accurately predict TB outcomes. Radiographic data independently obtained, interpreted by two experienced pulmonologists was collated with demographic details and, sputum smear and culture grades of participants by an independent statistician and analyzed using the Cox Proportional Hazards model, to not only adjust for confounding factors including treatment effect, but also explore the interaction between radiological and bacteriological parameters for better therapeutic application., Results: Of 667 TB patients with data available, cavitation, extent of involvement, lower zone involvement, smear and culture grade at baseline were significant parameters predisposing to an unfavorable TB treatment outcome in the univariate analysis. Reduction in radiological lesions in Chest X-ray by at least 50% at 2 months and 75% at the end of treatment helped in averting unfavorable responses. Smear and Culture conversion at the end of 2 months was highly significant as a predictor (p<0.001). In the multivariate analysis, the adjusted hazards ratios (HR) for an unfavorable response to TB therapy for extent of involvement, baseline cavitation and persistence (post treatment) were 1.21 (95% CI: 1.01-1.44), 1.73 (95% CI: 1.05-2.84) and 2.68 (95% CI: 1.4-5.12) respectively. A 3+ smear had an HR of 1.94 (95% CI: 0.81-4.64). Further probing into the interaction, among patients with 3+ and 2+ smears, HRs for cavitation were 3.26 (95% CI: 1.33-8.00) and 1.92 (95% CI: 0.80-4.60) while for >2 zones, were 3.05 (95% CI: 1.12-8.23) and 1.92 (95% CI: 0.72-5.08) respectively. Patients without cavitation, zonal involvement <2, and a smear grade less than 2+ had a better prognosis and constituted minimal disease., Conclusion: Baseline Cavitation, Opacities occupying >2 zones and 3+ smear grade individually and independently forecasted a poorer TB outcome. The interaction model revealed that Zonal involvement confined to 2 zones, without a cavity and smear grade up to 2+, constituting "minimal disease", had a better prognosis. Radiological clearance >50% along with smear conversion at the end of intensive phase of treatment, observed to be a reasonable alternative to culture conversion in predicting a successful outcome. These parameters may potentially take up key positions as stratification factors for future trials contemplating on shorter TB regimens., Competing Interests: The authors have declared that no competing interests exist.

Vacuolar myelinopathy is a fatal neurological disease that was initially discovered during a mysterious mass mortality of bald eagles in Arkansas in the United States. The cause of this wildlife disease has eluded scientists for decades while its occurrence has continued to spread throughout freshwater reservoirs in the southeastern United States. Recent studies have demonstrated that vacuolar myelinopathy is induced by consumption of the epiphytic cyanobacterial species Aetokthonos hydrillicola growing on aquatic vegetation, primarily the invasive Hydrilla verticillata Here, we describe the identification, biosynthetic gene cluster, and biological activity of aetokthonotoxin, a pentabrominated biindole alkaloid that is produced by the cyanobacterium A. hydrillicola We identify this cyanobacterial neurotoxin as the causal agent of vacuolar myelinopathy and discuss environmental factors-especially bromide availability-that promote toxin production., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Per- and polyfluoroalkyl substances (PFAS) are a widespread, environmentally persistent class of anthropogenic chemicals that are widely used in industrial and consumer products and frequently detected in environmental media. Potential human health impacts from long-term exposure to legacy PFAS resulted in the industrial development and use of numerous replacement species in recent decades. Environmental investigative activities have been crucial in identifying the existence and environmental transport of emerging PFAS in environmental media. Previous investigations in an industrially impacted region of southwestern New Jersey has shown consistently elevated levels of legacy PFAS, motivating additional examination by non-targeted mass spectrometry to identify emerging PFAS contamination. This study applied non-targeted analysis to water samples collected in Gloucester and Salem Counties in southwestern New Jersey, revealing the existence of a series of novel chloro-perfluoro-polyether carboxylates and related PFAS species originating from an industrial PFAS user in the region. There is sparse publicly available toxicity information for the emerging chemical species, but estimated concentrations exceeded the state drinking water standards for perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA). Non-targeted analysis was used to estimate the effectiveness of point-of-entry water treatment systems for removal of the emerging species and reduced the abundance of PFAS by >90%.

Background: The State of Ceará, in Northeastern Brazil, suffers from a triple burden of arboviruses (dengue, Zika and chikungunya). We measured the seroprevalence of chikungunya, dengue and Zika and its associated factors in the population of Juazeiro do Norte, Southern Ceará State, Brazil., Methods: A cross-sectional study of analytical and spatial analysis was performed to estimate the seroprevalence of dengue, Zika and chikungunya, in the year 2018. Participants were tested for IgM and IgG against these three viruses. Those with IgM and/or IgG positive tests results were considered positive. Poisson regression was used to analyze the factors associated with positive cases, in the same way that the spatial analysis of positive cases was performed to verify whether the cases were grouped., Results: Of the 404 participants, 25.0% (103/404) were positive for CHIKV, 92.0% (373/404) for flavivirus (dengue or Zika) and of these, 37.9% (153/404) samples were classified as probable dengue infection. Of those who reported having had an arbovirus in the past, positive CHIKV cases had 58.7% arthralgia (PR = 4.31; 95% CI: 2.06-9.03; p = 0.000) mainly in the hands, ankles and feet. Age over 60 years had a positive association with cases of flavivirus (PR = 1.29; 95% CI: 1.09-1.54; p = 0.000). Fever, muscle pain, joint pain and skin rash were the most reported symptoms (46.1, 41.0, 38.3 and 28.41%, respectively). The positive cases of chikungunya and dengue or Zika were grouped in space and the city center was most affected area., Conclusions: Four years after the introduction of CHIKV, where DENV has been in circulation for over 30 years, 1/4 of the population has already been exposed, showing the extent of the epidemic. The measured prevalence was much higher than that reported by local epidemiological surveillance.

Background: Adolescent vaping continues to rise, yet little is known about teen vape users beyond demographics. Effective intervention requires a deeper understanding of the psychographics and interests of adolescent vape users to facilitate targeted communication campaigns., Methods: We analyzed the 2017-2018 weighted cross-sectional online survey data from Virginia high school students (N = 1594) to identify and describe subgroups of adolescents who vaped. Participants reported 30-day vape use, identification with 5 peer crowds (Alternative, Country, Hip Hop, Mainstream, Popular), social prioritization, agreement with personal values statements, social media and smartphone use, and television and event preferences. We compared vaping rates and frequency by peer crowd using a chi-square analysis with follow-up testing to identify higher-risk crowds and confirmed associations using binary and multinomial logistic regression models with peer crowd scores predicting vaping, controlling for demographics. We then used chi-square and t tests to describe the psychographics, media use, and interests of higher-risk peer crowds and current vape users within those crowds., Results: Any current vaping was the highest among those with Hip Hop peer crowd identification (25.4%), then Popular (21.3%). Stronger peer crowd identification was associated with increased odds of any current vaping for both crowds, vaping on 1 to 19 days for both crowds, and vaping on 20 to 30 days for Hip Hop only. Compared with other peer crowds and non-users, Hip Hop and Popular youth and current vape users reported greater social prioritization and agreement with values related to being social and fashionable. Hip Hop and Popular youth and current vape users reported heavy Instagram and Snapchat use, as well as unique television show and event preferences., Conclusions: Hip Hop and Popular adolescents are most likely to vape and should be priority audiences for vaping prevention campaigns. Findings should guide the development of targeted health communication campaigns delivered via carefully designed media strategies., Competing Interests: Declaration of Conflicting Interests:The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article., (© The Author(s) 2020.)

The toxicity and environmental persistence of anthropogenic per- and poly-fluoroalkyl substances (PFAS) are of global concern. To address legacy PFAS concerns in the United States, industry developed numerous replacement PFAS that commonly are treated as confidential information. To investigate the distribution of PFAS in New Jersey, soils collected from across the state were subjected to nontargeted mass-spectral analyses. Ten chloroperfluoropolyether carboxylates were tentatively identified, with at least three congeners in all samples. Nine congeners are ≥(CF 2 ) 7 Distinct chemical formulas and structures, as well as geographic distribution, suggest airborne transport from an industrial source. Lighter congeners dispersed more widely than heavier congeners, with the most widely dispersed detected in an in-stock New Hampshire sample. Additional data were used to develop a legacy-PFAS fingerprint for historical PFAS sources in New Jersey., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Introduction: Chikungunya causes fever and severe and persistent joint pain., Methods: We reported a chikungunya outbreak that occurred in Ceará State, Brazil between 2016 and 2017 with emphasis on epidemiological characterization of cases, high number of deaths, mortality-associated factors, and spatial and temporal spread of the epidemic among municipalities., Results: In November 2015, the first autochthonous cases of chikungunya were confirmed in Ceará, Brazil. In 2016-2017, 195,993 cases were reported, with an incidence of 2,186.5/100,000 inhabitants and 244 confirmed deaths., Conclusions: Rapid transmission and high mortality rate are serious problems, especially in regions with co-circulating arboviruses.

In recent years, fluorotelomer-based polymers (FTPs) have been the dominant product of the fluorotelomer industry. For the last decade, whether FTPs degrade to toxic perfluorocarboxylates (PFCAs) has been vigorously contested, with early studies arguing that FTPs have half-lives >1000 years, and others concluding decadal half-lives. Given this FTP half-life discrepancy of 10- to >100-fold, here we investigate whether environmental loads of long-chain PFCAs might offer an independent approach to assess FTP half-lives. Specifically we: i) use surface soil-PFCA data to estimate terrestrial surface-soil background PFCA concentrations and loads; ii) extrapolate these data to generate global PFCA load estimates; iii) compare these estimates to published ocean-derived and industrial-emissions load estimates, finding agreement for perfluorooctanoate (C8), but an excess in longer-chain (C10,C12) PFCAs for ocean- and soil-derived loads relative to emissions; iv) model FTP degradation rates required to reconcile this discrepancy; and iv) compare our modeled estimates to existing experimental results. These findings show agreement for FTP half-lives at the decades-scale supporting existing laboratory studies that report decade-scale half-lives for FTPs. This suggests that global long-chain PFCA loads will increase for decades if legacy FTPs already manufactured are not contained upon disposal. These results suggest that FTPs comprised of novel poly- and perfluorinated alkyl substances (PFASs) now in production might constitute considerable sources to the environment of the new generation of PFASs., (Published by Elsevier B.V.)

Analytical data for ultra-high-performance liquid chromatography (UHPLC), nontargeted, high-resolution, mass-spectrometry (HR/MS) molecular features from a wide array of samples are used to calculate 13 C 1 12 C (n-1) / 12 C n isotopologue ratios. These ratios increase with molecular carbon number roughly following a trend defined by atmospheric carbon. When the effective source reservoir 13 C/ 12 C ratio is calculated from the isotopologue ratio (assuming a fractionation factor of unity), features in biotic samples uniformly are tightly grouped, proximate to atmospheric 13 C/ 12 C ratio. In contrast, features in soil natural organic matter (NOM), dust NOM and anthropogenic compounds range from proximate to relatively divergent from atmospheric 13 C/ 12 C. For the NOM, 13 C/ 12 C ratios are consistent with an expected preferential volatilization of 12 C, rendering features in soil NOM 13 C-enriched and some features in dust NOM 13 C-depleted. Anthropogenic compounds tend to diverge most dramatically from atmospheric 13 C/ 12 C, generally toward 13 C-depletion, but pesticides we tested tended toward 13 C-enriched. This pattern is robust and evident in: i) anthropogenic vs natural features in dust; ii) perfluorinated compounds in standards and as soil contaminants; and iii) sunscreen compounds in commercial products and wastewater. Considering the observed wide 13 C/ 12 C range for anthropogenic compounds, we suggest Rayleigh distillation during synthetic processes commonly favors one isotope over the other, rendering a source reservoir that is progressively depleted as synthesis proceeds and, consequently, generates a wide variation in 13 C/ 12 C for man-made products. However, kinetic-isotopic effects and/or synthesis from petroleum/natural gas might contribute to the anthropogenic isotopic signature as well. Regardless of cause, 13 C/ 12 C can be used to cull HR/MS molecular features that are more likely to be of anthropogenic or non-biotic origin., (Published by Elsevier B.V.)

Background: Chikungunya virus infection in neonates is relatively rare and can lead to death., Case Presentation: We report the occurrence of the first death of a mother and child after probable vertical transmission of chikungunya virus in Brazil. A 28-year-old pregnant woman with hypertension presented with symptoms compatible with an arboviral disease at 34 weeks' gestation. She developed preeclampsia with severe respiratory failure which resulted in the emergency cesarean section, and the patient died 12 days after the onset of symptoms. The pre-term newborn weighed 2535 g, with an Apgar score of 4/8. He was referred to the neonatal ICU with neutrophilia and thrombocytopenia, several seizure episodes, and hemorrhagic disorders, which resulted in death. Chikungunya IgM antibody was detected in the cerebrospinal fluid., Conclusions: We present the first documented maternal and neonatal death in Brazil after probable chikungunya infection during pregnancy.

The distribution of 32 per/polyfluoroalkyl substances (PFASs) in surface soils was determined at 62 locations representing all continents (North America n = 33, Europe n = 10, Asia n = 6, Africa n = 5, Australia n = 4, South America n = 3 and Antarctica n = 1) using ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) systems. Quantifiable levels of perfluoroalkyl carboxylates (PFCAs: PFHxA-PFTeDA) were observed in all samples with total concentrations ranging from 29 to 14,300 pg/g (dry weight), while perfluoroalkane sulfonates (PFSAs: PFHxS, PFOS and PFDS) were detected in all samples but one, ranging from

Perfluoroalkyl substances are globally distributed in both urban and remote settings, and routinely are detected in wildlife, humans, and the environment. One of the most prominent and routinely detected perfluoroalkyl substances is perfluorooctanoic acid (PFOA), which has been shown to be toxic to both humans and animals. PFOA exists as both linear and branched isomers; some of the branched isomers are chiral. A novel GC-NCI-MS method was developed to allow for isomer/enantiomer separation, which was achieved using two columns working in tandem; a 30-m DB-5MS column and a 30-m BGB-172 Analytik column. Samples were derivatized with diazomethane to form methyl esters of the PFOA isomers. In standards, at least eight PFOA isomers were detected, of which at least four were enantiomers of chiral isomers; one chiral isomer (P3) was sufficiently separated to allow for enantiomer-fraction calculations. Soil, sediment and plant samples from contaminated locations in Alabama and Georgia were analyzed. P3 was observed in most of these environmental samples, and was non-racemic in at least one sediment, suggesting the possibility of chirally selective generation from precursors or enantioselective sorption. In addition, the ratio of P3/linear PFOA was inversely related to distance from source, which we suggest might reflect a higher sorption affinity for the P3 over the linear isomer. This method focuses on PFOA, but preliminary results suggest that it should be broadly applicable to other chiral and achiral perfluorocarboxylic acids (PFCAs); e.g., we detected several other homologous PFCA isomers in our PFCA standards and some environmental samples., (Published by Elsevier Ltd.)

Fluorotelomer-based polymers (FTPs) are the main product of the fluorotelomer industry. For nearly 10 years, whether FTPs degrade to form perfluorooctanoate (PFOA) and perfluorocarboxylate (PFCA) homologues has been vigorously contested. Here we show that circum-neutral abiotic hydrolysis of a commercial FTP proceeds with half-life estimates of 55-89 years and that base-mediated hydrolysis overtakes neutral hydrolysis at about pH = 10, with a half-life of ~0.7 years at pH ∼ 12. Considered in light of the large production volume of FTPs and the poor efficacy of conventional treatments for recovery of PFCAs from waste streams, these results suggest that FTPs manufactured to date potentially could increase PFCAs 4- to 8-fold over current oceanic loads, largely depending on the integrity of disposal units to contain PFCAs upon hydrolytic generation from FTPs.

A pair of homologous series of polyfluorinated degradation products have been identified, both having structures similar to perfluorocarboxylic acids but (i) having a H substitution for F on the α carbon for 2H polyfluorocarboxylic acids (2HPFCAs) and (ii) bearing a double bond between the α-β carbons for the unsaturated PFCAs (2uPFCAs). Obtaining an authentic sample containing 2uPFOA and 2HPFOA, we optimized a mass-spectrometric multiple-reaction-monitoring (MS/MS) technique and then identified uPFCA and HPFCA homologous series in sludge-applied agricultural soils and fodder grasses for cattle grazing. Analysis of samples from a degradation experiment of commercial fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, confirmed that commercial FTPs are a potential source of uPFCAs and HPFCAs to the environment. We further confirmed the identity of the uPFCAs by imposing high-energy ionization to decarboxylate the uPFCAs then focused on the fluorinated chains in the first MS quadrupole. We also employed this high-energy ionization to decarboxylate and analyze PFCAs by MS/MS (for the first time, to our knowledge). In exploratory efforts, we report the possible detection of unsaturated perfluorooctanesulfonate in environmental samples, having a conceptual double-bond structure analogous to uPFOA. Using microcosms spiked with fluorotelomer compounds, we found 2uPFOA and 2HPFOA to be generated from unsaturated 8:2 fluorotelomer acid (8:2 FTUCA) and propose β- and α-oxidation mechanisms for generation of these compounds from 8:2 FTUCA. In light of these experimental results, we also reexamined the proposed biodegradation pathways of 8:2 fluorotelomer alcohol.

The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) which have values assigned for legacy organic pollutants and toxic elements. Existing SRMs serve as homogenous materials that can be used for method development, method validation, and measurement for contaminants that are now of concern. NIST and multiple groups have been measuring the mass fraction of a group of emerging contaminants, polyfluorinated substances (PFASs), in a variety of SRMs. Here we report levels determined in an interlaboratory comparison of up to 23 PFASs determined in five SRMs: sediment (SRMs 1941b and 1944), house dust (SRM 2585), soil (SRM 2586), and sludge (SRM 2781). Measurements presented show an array of PFASs, with perfluorooctane sulfonate being the most frequently detected. SRMs 1941b, 1944, and 2586 had relatively low concentrations of most PFASs measured while 23 PFASs were at detectable levels in SRM 2585 and most of the PFASs measured were at detectable levels in SRM 2781. The measurements made in this study were used to add values to the Certificates of Analysis for SRMs 2585 and 2781.

Fluorotelomer-based polymers (FTPs) are the primary product of the fluorotelomer industry. Here we report on a 376-day study of the degradability of two commercial acrylate-linked FTPs in four saturated soils and in water. Using an exhaustive serial extraction, we report GC/MS and LC/MS/MS results for 50 species including fluorotelomer alcohols and acids, and perfluorocarboxylates. Modeling of seven sampling rounds, each consisting of ≥5 replicate microcosm treatments, for one commercial FTP in one soil yielded half-life estimates of 65–112 years and, when the other commercial FTP and soils were evaluated, the estimated half-lives ranged from 33 to 112 years. Experimental controls, consisting of commercial FTP in water, degraded roughly at the same rate as in soil. A follow-up experiment, with commercial FTP in pH 10 water, degraded roughly 10-fold faster than the circum-neutral control suggesting that commercial FTPs can undergo OH–-mediated hydrolysis. 8:2Fluorotelomer alcohol generated from FTP degradation in soil was more stable than without FTP present suggesting a clathrate guest–host association with the FTP. To our knowledge, these are the only degradability-test results for commercial FTPs that have been generated using exhaustive extraction procedures. They unambiguously show that commercial FTPs, the primary product of the fluorotelomer industry, are a source of fluorotelomer and perfluorinated compounds to the environment.

Fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, are antistaining and antiwetting agents that permeate the products and surfaces of modern society. However, the degree to which these materials expose humans and the environment to fluorotelomer and perfluorinated compounds, including recalcitrant and toxic compounds such as perfluorooctanoic acid (PFOA), is ill-defined. The design intent of FTPs, to minimize interaction with other substances, including solvents, heretofore has stymied efforts to develop robust methods to characterize the content of monomers and associated compounds of new commercial FTPs, as well as commercial FTPs that have been aged in environmental media for degradation testing. Here we show that FTPs can be exhausted of these compounds and quantitated by (i) drying the FTP on a suitable substrate at elevated temperature to achieve low, constant monomer concentrations; (ii) serial extraction with MTBE for fluorotelomer-monomer analysis by GC/MS in PCI mode; followed by (iii) serial extraction with 90/10 ACN/H2O for polyfluorocompound analysis by LC/MS/MS in negative ESI mode. This approach yields exhaustive, internally consistent accounting of monomers and associated compounds for FTPs, either alone or in a soil matrix (representing an environmental medium), for both new and simulated-aged FTPs to allow degradation testing, and for fluorinated compounds at least as long as C12.

Concentrations of perfluorinated chemicals (PFCs) were measured in surface waters and sediments from the Coosa River watershed in northwest Georgia, USA, to examine their distribution downstream of a suspected source. Samples from eight sites were analyzed using liquid chromatography-tandem mass spectrometry. Sediments were also used in 28-d exposures with the aquatic oligochaete, Lumbriculus variegatus, to assess PFC bioaccumulation. Concentrations of PFCs in surface waters and sediments increased significantly below a land-application site (LAS) of municipal/industrial wastewater and were further elevated by unknown sources downstream. Perfluorinated carboxylic acids (PFCAs) with eight or fewer carbons were the most prominent in surface waters. Those with 10 or more carbons predominated sediment and tissue samples. Perfluorooctane sulfonate (PFOS) was the major homolog in contaminated sediments and tissues. This pattern among sediment PFC concentrations was consistent among sites and reflected homolog concentrations emanating from the LAS. Concentrations of PFCs in oligochaete tissues revealed patterns similar to those observed in the respective sediments. The tendency to bioaccumulate increased with PFCA chain length and the presence of the sulfonate moiety. Biota-sediment accumulation factors indicated that short-chain PFCAs with fewer than seven carbons may be environmentally benign alternatives in aquatic ecosystems; however, sulfonates with four to seven carbons may be as likely to bioaccumulate as PFOS., (Copyright © 2011 SETAC.)

Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes in plants from biosolid-amended fields. Dichloromethane-methanol and ethylacetate were chosen as extracting solutions for PFCs and FTOHs, respectively. Nine perfluorocarboxylic acids (PFCAs), three perfluorosulfonic acids (PFSAs), and ten FTOHs were monitored. Most PFCAs and perfluorooctanesulfonate (PFOS) were quantifiable in plants grown in contaminated soils, whereas PFCs went undetected in plants from two background fields. Perfluorooctanoic acid (PFOA) was a major homologue (∼10-200 ng/g dry wt), followed by perfluorodecanoic acid (∼3-170 ng/g). [PFOS] in plants (1-20 ng/g) generally was less than or equal to most [PFCAs]. The site-specific grass/soil accumulation factor (GSAF = [PFC](Grass)/[PFC](Soil)) was calculated to assess transfer potentials from soils. Perfluorohexanoic acid had the highest GSAF (= 3.8), but the GSAF decreased considerably with increasing PFCA chain length. Log-transformed GSAF was significantly correlated with the PFCA carbon-length (p < 0.05). Of the measured alcohols, 8:2nFTOH was the dominant species (≤1.5 ng/g), but generally was present at ≥10× lower concentrations than PFOA.

Sludges generated at a wastewater treatment plant (WWTP) in Decatur, Alabama have been applied to agricultural fields for more than a decade. Waste-stream sources to this WWTP during this period included industries that work with fluorotelomer compounds, and sludges from this facility have been found to be elevated in perfluoroalkylates (PFAs). With this knowledge, the U.S. Environmental Protection Agency collected soil samples from sludge-applied fields as well as nearby "background" fields for PFA analysis. Samples from the sludge-applied fields had PFAs at much higher concentrations than in the background fields; generally the highest concentrations were perfluorodecanoic acid (≤ 990 ng/g), perfluorododecanoic acid (≤ 530 ng/g), perfluorooctanoic acid (≤ 320 ng/g), and perfluorooctane sulfonate (≤ 410 ng/g). Contrasts in PFA concentration between surface and deeper soil samples tended to be more pronounced in long-chain congeners than shorter chains, perhaps reflecting relatively lower environmental mobilities for longer chains. Several PFAs were correlated with secondary fluorotelomer alcohols (sec-FTOHs) suggesting that PFAs are being formed by degradation of sec-FTOHs. Calculated PFA disappearance half-lives for C6 through C11 alkylates ranged from about 1 to 3 years and increase with increasing chain-length, again perhaps reflecting lower mobility of the longer-chained compounds.

Soil samples were collected for fluorotelomer alcohol (FTOH) analyses from six fields to which sludge had been applied and one "background" field that had not received sludge. Ten analytes in soil extracts were quantified using GC/MS. Sludge-applied fields had surface soil FTOH concentrations exceeding levels found in the background field. For 8:2nFTOH, which can degrade to perfluorooctanoic acid, impacted surface-soils ranged from 5 to 73 ng/g dry weight, clearly exceeding the background field in which 8:2nFTOH was not detected. The highest [FTOH] generally was 10:2nFTOH, which had concentrations of <5.6 to 166 ng/g. For the first time, we document the persistence of straight-chained primary FTOHs (n-FTOHs) and branch-chained secondary FTOHs (sec-FTOHs), which are transformation products of n-FTOHs, in field soils for at least five years after sludge application. Ratios of sec-FTOHs to n-FTOHs were highest for 7:2sFTOH/8:2nFTOH (∼50%) and decreased with increasing chain length to a minimum for the longest-chained analytes, 13:2sFTOH/14:2nFTOH (∼10%). Disappearance half-lives for FTOHs, calculated with these data, ranged from 0.85 to 1.8 years. These analytical results show that the practice of sludge application to land is a pathway for the introduction of FTOHs and, accordingly, their transformation products, perfluorocarboxylic acids, into the environment.

A fast, rigorous method was developed to maximize the extraction efficacy for ten perfluorocarboxylic acids and perfluorooctanesulfonate from waste-water-treatment sludge and to quantitate using liquid chromatography, tandem-mass spectrometry (LC/MS/MS). First, organic solvents were tested for extraction efficiency, including acetonitrile (ACN), methanol (MeOH), isopropanol (IPA), tetrahydrofuran (THF), and 50/50 ACN/MeOH (v/v). Among the extractants tested, 50/50 ACN/MeOH yielded the best results for our combined criteria of extraction efficacy and solvent-handling convenience. Second, chemical pretreatment prior to solvent extraction was tested with sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrochloric acid (HCl), and potassium persulfate (K(2)S(2)O(8)). Pretreatment with NaOH and HCl effectively recovered additional PFCs from the sludge, but KOH and K(2)S(2)O(8) digestion were less effective than no pretreatment. Third, cleanup methods were investigated with solid-phase extraction using HLB (hydrophilic-lipophilic balanced) and WAX (weak-anion exchange) stationary phases, and with ion-pairing. The HLB stationary phase yielded a slight edge over the other two cleanup strategies in terms of recoverable PFCs and chromatographic separation. Finally, the appropriateness of isotopically labeled PFCs for quantitating unlabeled PFCs using isotopic dilution in complex sludge extracts was evaluated by comparison to results obtained with the standard-addition method. A National Institute of Standards and Technology (NIST) domestic sludge (CRM 2781) was analyzed using our finalized method and compared with previously reported results.

Fluorotelomer polymers are used in a broad array of products in modern societies worldwide and, if they degrade at significant rates, potentially are a significant source of perfluorooctanoic acid (PFOA) and related compounds to the environment To evaluate this possibility, we incubated an acrylate-linked fluorotelomer polymer in soil microcosms and monitored the microcosms for possible fluorotelomer (FT) and perfluorinated-compound (PFC) degradation products using GC/MS and LC/MS/MS. This polymer scavenged FTs and PFCs aggressively necessitating development of a multistep extraction using two solvents. Aged microcosms accumulated more FTs and PFCs than were present in the fresh polymer indicating polymer degradation with a half-life of about 870-1400 years for our coarse-grained test polymer. Modeling indicates that more-finely grained polymers in soils might have half-lives of about 10-17 years assuming degradation is surface-mediated. In our polymer-soil microcosms, PFOA evidently was lost with a half-life as short as 130 days, possibly by polymer-catalyzed degradation. These results suggest that fluoratelomer-polymer degradation is a significant source of PFOA and other fluorinated compounds to the environment.

This article describes the development of an analytical method for the determination of fluorotelomer alcohols (FTOHs) in soil. The sensitive and selective determination of the telomer alcohols was performed by extraction with methyl tert-butyl ether (MTBE) and analysis of the extract using gas chromatography with detection and quantification by mass spectrometry operated in the positive chemical ionization mode. The protonated molecular ion, [M+H](+) and a fragment ion (loss of HF+H(2)O) m/z 38 less than the molecular ion were monitored to identify tentatively FTOHs in MTBE extracts of contaminated soils. The FTOHs were confirmed by treatment of the extract with a silylation reagent and observing the disappearance of the FTOH response and the appearance of peaks attributable to the [M+H](+) ions of the trimethylsilyl derivatives. Mass-labeled FTOHs were used as recovery and matrix internal standards. Recovery experiments on soils shown to be free of endogenous FTOHs at instrument detection limits (IDL) of 16 fg/microL for 6:2 FTOH, 10 fg/microL for 8:2 FTOH and 14 fg/microL for 10:2 FTOH yielded a limit of quantitation (LOQ) of 190, 100, and 160 fg/microL for 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH, respectively when 3 g samples of soil were extracted with 1 mL MTBE. The levels of the 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH in five soils contaminated with FTOHs by exposure to the laboratory atmosphere during air drying were determined. In these air-dried soils, concentrations of FTOHs ranged from non-detectable to 3600 fg/microL (0.6 ng/g) of the 6:2 FTOH in the extract of a commercial topsoil. This method was used to determine even and odd numbered FTOHs from 6:2 through 14:2 in soils from fields that had received applications of sewage sludge. Concentrations of FTOHs in these sludge-applied soils ranged as high as 820 ng/g of dry soil for the 10:2 FTOH.

The purpose of this study was to assess the relationship between mode of delivery and maternal complications, based on a retrospective cohort of all births at a public hospital in 2003. Complications included: infection, hemorrhage, hysterectomy, uterine rupture, lesions in adjacent organs, deep venous thrombosis, and pulmonary embolism. The analysis used odds ratio (OR), chi-squared test, and Fisher's exact test, besides logistic regression. Fifteen complications were identified. Taking vaginal delivery as the reference, an association was found between cesarean section and overall complications. Analysis of confounding showed an association between hypertension, HIV, placenta previa, and abruptio placentae. After controlling for these variables, an association remained between overall complications and cesarean section (OR = 9.7; p = 0.04). Another analysis comparing elective cesareans and vaginal deliveries also showed an increased risk for cesarean (OR = 4.7; p = 0.02). Finally, comparing elective cesareans with trial of labor, we found an increased proportion of complications in elective cesareans, with borderline significance (OR = 3; p = 0.058). We concluded that cesarean section is associated with maternal morbidity, even after controlling for confounders.

With the objective of detecting and quantitating low concentrations of perfluorinated carboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA), in soils, we compared the analytical suitability of liquid chromatography columns containing three different stationary phases, two different liquid chromatography-tandem mass spectrometry (LC/MS/MS) systems, and eight combinations of sample-extract pretreatments, extractions and cleanups on three test soils. For the columns and systems we tested, we achieved the greatest analytical sensitivity for PFCAs using a column with a C(18) stationary phase in a Waters LC/MS/MS. In this system we achieved an instrument detection limit for PFOA of 270 ag/microL, equating to about 14 fg of PFOA on-column. While an elementary acetonitrile/water extraction of soils recovers PFCAs effectively, natural soil organic matter also dissolved in the extracts commonly imparts significant noise that appears as broad, multi-nodal, asymmetric peaks that coelute with several PFCAs. The intensity and elution profile of this noise is highly variable among soils and it challenges detection of low concentrations of PFCAs by decreasing the signal-to-noise contrast. In an effort to decrease this background noise, we investigated several methods of pretreatment, extraction and cleanup, in a variety of combinations, that used alkaline and unbuffered water, acetonitrile, tetrabutylammonium hydrogen sulfate, methyl-tert-butyl ether, dispersed activated carbon and solid-phase extraction. For the combined objectives of complete recovery and minimization of background noise, we have chosen: (1) alkaline pretreatment; (2) extraction with acetonitrile/water; (3) evaporation to dryness; (4) reconstitution with tetrabutylammonium-hydrogen-sulfate ion-pairing solution; (5) ion-pair extraction to methyl-tert-butyl ether; (6) evaporation to dryness; (7) reconstitution with 60/40 acetonitrile/water (v/v); and (8) analysis by LC/MS/MS. Using this method, we detected in all three of our test soils, endogenous concentrations of all of our PFCA analytes, C(6) through C(10)-the lowest concentrations being roughly 30 pg/g of dry soil for perfluorinated hexanoic and decanoic acids in an agricultural soil.

Methods were developed for the extraction from soil, identification, confirmation and quantitation by LC/MS/MS of trace levels of perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA). Whereas PFOA, PFNA and PFDA all can be quantitated using the method of standard additions, PFOA also can be quantitated less laboriously using 13C4-PFOA as a matrix internal standard. The impact of extract matrices on signal varied between soils and temporally during analytical runs rendering 13C4-PFOA unsuitable as a matrix internal standard for quantitating perfluorinated carboxylic acids (PFCAs) other than PFOA, which co-elutes with 13C4-PFOA. In fact, for soil extracts, quantitation of PFCAs based on external calibrations proved about as accurate as use of matrix internal standards for target analytes that do not co-elute with the matrix internal standard. Also, 13C4-PFOA should be used carefully as a matrix internal standard for trace levels of PFOA because some 13C4-PFOA standards contain trace impurities of unlabelled PFOA. When the presence of PFCAs in soil extracts is being determined by LC/MS/MS, detection limits are best defined by statistical methods that quantify the significance of contrast between analytical signal and background noise using multiple analyses. Further, when developing a calibration of low concentrations using weighted regression, the central tendency of the calibration line is best fitted using graphical depictions of error. As the MDL for the transition-product quantitation ion is approached in LC/MS/MS, relatively weak signals of transition-product confirmation ions can be used as a rejection criterion by looking for anomalously high values of the ratio of the confirmation to the quantitation ion.

Perfluorocarboxylic acids (PFCAs), namely perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA), have been identified as persistent, bioaccumulative and potentially toxic compounds. The structural analog, 8-2 fluorotelomer alcohol (8-2 fTOH) is considered the probable precursor of these stable metabolites. Because simultaneous quantification is needed for volatile and non-volatile perfluorinated chemicals (PFCs) in complex matrices, a GC/MS method was developed and tested based on selected ion monitoring of perfluorinated alkyl parent chain fragment ions. Although the method requires a derivatization step, combined GC/MS analysis of PFCA-me's and FTOHs increases analytical efficiency and decreases sample analysis time. The method instrument detection limits are between 7.1 and 24.5 ng/mL extract (MTBE), and the method quantification limits are below 50 ng/mL serum or ng/g liver for all PFCs investigated. Recoveries from mouse serum and liver homogenates, which were spiked with FTOHs and PFCAs at levels of 25 and 200 ng/mL or ng/g, ranged from 81 to 101%. Finally, the utility of the method was demonstrated by dosing male CD-1 mice with 30 mg/kg-BW of 8-2 fTOH and quantifying PFCs 6h post-treatment. The advantages of this method are (1) the simultaneous detection of both volatile and non-volatile fluorotelomer-based chemicals in complex matrices, such as mammalian tissues, (2) as a confirmatory method to LC-MS/MS, and (3) as an alternative method of analysis for laboratories without access to LC-MS/MS.

The persistence and fate of organic contaminants in the environment largely depends on their rate of degradation. Most studies of degradation rate are performed in the lab where chemical conditions can be controlled precisely. Unfortunately, literature values for lab degradation studies often are orders of magnitude higher than for field-generated studies, calling into question the relevance of lab-generated values for characterizing the persistence of organic contaminants in the environment. Complicating analysis of this ostensible disparity between lab and field degradation values, field-generated values often do not account for effects of adsorption. Modeling with a newly derived analytical solution for first-order degradation coupled with advective losses and adsorption to solve for degradation constants is insensitive to uncertainties in field properties. Application to field data shows that accounting for advection and adsorption greatly affects the value of calculated degradation constants compared to disappearance constants, which do not account for these phenomena. In fact, degradation constants, calculated using these analytical solutions and field data, are in the range reported for lab-generated data. Using these analytical solutions, for the sulfate-reducing field conditions documented for this site, perchloroethene, trichloroethene, 1,1,1-trichloroethane, 1,1-dichloroethane, and chloroethane all degraded with half-lives ranging from 5 to 115 d. Consistent with other studies of sulfate-reducing conditions, cis-1,2-dichloroethene did not chemically degrade at a measurable rate. When nonaqueous phase 1,1-dichloroethane is present, down-gradient concentrations vary in an annual sinusoidal pattern, apparently because of seasonal variation in dilution from groundwater recharge.

The second of twins males expired of respiratory insufficiency shortly after birth. Unusual facial appearance included prominent forehead, flat nasal bridge, widely separated inner canthi, downward slanting eyes with narrow palpebral fissures, epicanthic folds, small mouth and micrognathia, and apparently low-set ears; there was also cryptorchidism bilaterally and a simian crease bilaterally. The pregnancy of the 19-year-old black woman was not unusual, but polyhydramnios accompanied the delivery of this twin. The twin placentae were diamniotic and monochorionic, one being slightly immature with a two-vessel cord. We interpreted the karyotype as 46,XY,del(10) (p11-15): The brother and parents were normal. The dysmorphic features of this and three previously reported cases of 10p- do not permit definition of a syndrome. These are apparently the first monozygous twins presenting discordance of chromosomal structure; previously reported chromosomal discordance in monozygous twins involved numerical abnormality. Considering that the mechanism monozygous twinning is not understood, we note that the occurrence of both twinning and a structural aberration in one of the twins suggests the possibility of a common cause.